U.S. patent number 10,407,541 [Application Number 15/564,524] was granted by the patent office on 2019-09-10 for block co-condensates of polysiloxanes and dihydroxydiphenylcycloalkane-based n (co)polycarbonates.
This patent grant is currently assigned to Covestro Deutschland AG. The grantee listed for this patent is Covestro Deutschland AG. Invention is credited to Klaus Horn, Alexander Meyer.
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United States Patent |
10,407,541 |
Meyer , et al. |
September 10, 2019 |
Block co-condensates of polysiloxanes and
dihydroxydiphenylcycloalkane-based n (CO)polycarbonates
Abstract
The present invention relates to block cocondensates of
polysiloxanes and dihydroxydiarylcycloalkane-based
(co)polycarbonates and also to a process for preparing such block
cocondensates. The invention further relates to the use of these
block cocondensates for producing mouldings and extrudates.
Inventors: |
Meyer; Alexander (Dusseldorf,
DE), Horn; Klaus (Dormagen, DE) |
Applicant: |
Name |
City |
State |
Country |
Type |
Covestro Deutschland AG |
Leverkusen |
N/A |
DE |
|
|
Assignee: |
Covestro Deutschland AG
(Leverkusen, DE)
|
Family
ID: |
52814868 |
Appl.
No.: |
15/564,524 |
Filed: |
April 4, 2016 |
PCT
Filed: |
April 04, 2016 |
PCT No.: |
PCT/EP2016/057326 |
371(c)(1),(2),(4) Date: |
October 05, 2017 |
PCT
Pub. No.: |
WO2016/162301 |
PCT
Pub. Date: |
October 13, 2016 |
Prior Publication Data
|
|
|
|
Document
Identifier |
Publication Date |
|
US 20180079862 A1 |
Mar 22, 2018 |
|
Foreign Application Priority Data
|
|
|
|
|
Apr 7, 2015 [EP] |
|
|
15162554 |
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08L
83/10 (20130101); C08G 77/448 (20130101); C08G
81/00 (20130101); C08G 81/027 (20130101); C08G
64/186 (20130101); C08L 69/00 (20130101) |
Current International
Class: |
C08G
64/18 (20060101); C08G 81/02 (20060101); C08G
81/00 (20060101); C08G 77/448 (20060101); C08L
83/10 (20060101); C08L 69/00 (20060101) |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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334782 |
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Mar 1921 |
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DE |
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3842931 |
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Jun 1990 |
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DE |
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19539290 |
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Apr 1997 |
|
DE |
|
19710081 |
|
Sep 1998 |
|
DE |
|
102007011069 |
|
Sep 2008 |
|
DE |
|
102008019503 |
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Oct 2009 |
|
DE |
|
0110221 |
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Jun 1984 |
|
EP |
|
0110238 |
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Jun 1984 |
|
EP |
|
122535 |
|
Oct 1984 |
|
EP |
|
0374635 |
|
Jun 1990 |
|
EP |
|
0500496 |
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Aug 1992 |
|
EP |
|
0716919 |
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Jun 1996 |
|
EP |
|
0839623 |
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May 1998 |
|
EP |
|
1308084 |
|
May 2003 |
|
EP |
|
WO-9615102 |
|
May 1996 |
|
WO |
|
Other References
International Search Report for PCT/EP2016/057326 dated Jun. 3,
2016. cited by applicant .
Written Opinion of the International Searching Authority for
PCT/EP2016/057326 dated Jun. 3, 2016. cited by applicant .
Zhou, W., et al., "Siloxane modification of polycarbonate for
superior flow and impact toughness", Polymer, 2010, pp. 1990-1999.
cited by applicant.
|
Primary Examiner: Buttner; David J
Attorney, Agent or Firm: Drinker Biddle & Reath LLP
Claims
The invention claimed is:
1. A block cocondensate comprising (A) 1-80 wt % of structural
units of the general formula (1), based on the total weight of the
block cocondensate, ##STR00013## in which R.sup.1 and R.sup.2
independently of one another are hydrogen, halogen, C.sub.1-C.sub.8
alkyl, C.sub.5-C.sub.6 cycloalkyl, phenyl or C.sub.7-C.sub.12
aralkyl, R.sup.3 and R.sup.4 for each X are individually selectable
and independently of one another are hydrogen or C.sub.1-C.sub.6
alkyl, and n is an integer from 4 to 7, X is carbon, with the
proviso that on at least one atom X R.sup.3 and R.sup.4 are
C.sub.1-C.sub.6 alkyl; (B) siloxane blocks of the general formula
(2) ##STR00014## where R.sup.5 is H, R.sup.6 and R.sup.7 are each
methyl, V is O, W is a single bond, Y is isopropylidene, m is an
average number of repeat units from 2 to 5, o is an average number
of repeat units from 10 to 100, q is 0, and p is 0 or 1; and the
product of m times o is a number between 15 and 200, and (C)
homopolycarbonate blocks which contain no structural units of the
formula (1) and have a number-average molecular weight M.sub.n of
at least 2000 g/mol.
2. The block cocondensate according to claim 1, wherein the
homopolycarbonate blocks derive from a homopolycarbonate obtained
by the melt transesterification process.
3. The block cocondensate according to claim 1, wherein the
homopolycarbonate blocks (C) are based on bisphenol A.
4. The block cocondensate according to claim 1, comprising
copolycarbonate blocks which contain the structural units of the
general formula (1).
5. The block cocondensate according to claim 4, wherein the
copolycarbonate blocks further have structural units which derive
from a diphenol of the formula (3) ##STR00015## in which R.sup.8
and R.sup.9 independently of one another are H, C.sub.1-C.sub.18
alkyl, C.sub.1-C.sub.18 alkoxy, halogen or optionally substituted
aryl or aralkyl, and Z is a single bond, --CO--, --O--, C.sub.1 to
C.sub.6 alkylene, C.sub.2 to C.sub.5 alkylidene, is a C.sub.5 to
C.sub.6 cycloalkylidene radical which may be substituted one or
more times by C.sub.1 to C.sub.4 alkyl, or is C.sub.6 to C.sub.12
arylene, which may be fused to a further aromatic ring containing
heteroatoms.
6. The block cocondensate according to claim 4, wherein the
copolycarbonate blocks further have structural units which derive
from bisphenol A.
7. The block cocondensate according to claim 1, wherein the
fraction of the siloxane blocks of the formula (2) in the block
cocondensate is 0.5 to 20.0 wt %, based on the total weight of the
block cocondensate.
8. Process for preparing the block cocondensate according to claim
1, comprising the reaction of (a) a (co)polycarbonate comprising
structural units of the general formula (1) (b) a
hydroxyaryl-terminated polysiloxane of the formula (2b)
##STR00016## where R.sup.5, R.sup.6, R.sup.7, V, W, Y, o, p, q and
m have the same definition as in formula (2) according to claim 1;
(c) and a homopolycarbonate in the melt.
9. The process according to claim 8, wherein the homopolycarbonate
has been prepared by the melt transesterification process.
10. The process according to claim 8, wherein the homopolycarbonate
has a number-average molecular weight of at least 2000 g/mol, and
an OH end group content of 300 to 900 ppm.
11. The process according to claim 8, wherein components (a) to (c)
are present in the following amounts in the melt: (a) 20 to 94.5 wt
% of the (co)polycarbonate, (b) 0.5 to 20 wt % of the
hydroxyaryl-terminated polysiloxane, and (c) 5 to 79.5 wt % of the
homopolycarbonate, based in each case on the total weight of the
melt.
12. The process according to claim 8, wherein the homopolycarbonate
is based on bisphenol A and the copolycarbonate is based on
bisphenol A and bisphenol TMC.
13. The block cocondensate according to claim 1, obtained by
reacting (a) a (co)polycarbonate comprising structural units of the
general formula (1) ##STR00017## in which R.sup.1 and R.sup.2
independently of one another are hydrogen, halogen, C.sub.1-C.sub.8
alkyl, C.sub.5-C.sub.6 cycloalkyl, phenyl or C.sub.7-C.sub.12
aralkyl, R.sup.3 and R.sup.4 for each X are individually selectable
and independently of one another are hydrogen or C.sub.1-C.sub.6
alkyl, and n is an integer from 4 to 7, X is carbon, with the
proviso that on at least one atom X R.sup.3 and R.sup.4 are
C.sub.1-C.sub.6 alkyl; (b) a hydroxyaryl-terminated polysiloxane of
the formula (2b) ##STR00018## R.sup.5 is H, R.sup.6 and R.sup.7 are
each methyl, V is O, W is a single bond, Y is isopropylidene, m is
an average number of repeat units from 2 to 5, o is an average
number of repeat units from 10 to 100, q is 0, and p is 0 or 1; and
the product of m times o is a number between 15 and 200; and (c)
and a homopolycarbonate which contains no structural units of the
formula (1) and has a number-average molecular weight M.sub.n of at
least 2000 g/mol in the melt.
14. A method comprising utilizing the block cocondensates according
to claim 1 for producing mouldings and extrudates.
15. A moulding or extrudate comprising a block cocondensate
according to claim 1.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a national stage application (under 35 U.S.C.
.sctn. 371) of PCT/EP2016/057326, filed Apr. 4, 2016, which claims
benefit of European Application No. 15162554.8, filed Apr. 7, 2015,
both of which are incorporated herein by reference in their
entirety.
The present invention relates to block cocondensates of
polysiloxanes and dihydroxydiarylcycloalkane-based
(co)polycarbonates and also to a process for preparing such block
cocondensates. The invention further relates to the use of these
block cocondensates for producing mouldings and extrudates.
BACKGROUND OF THE INVENTION
It is known that polysiloxane-polycarbonate block cocondensates
exhibit good properties in respect of low-temperature impact
strength and low-temperature notched-impact strength, chemical
resistance and outdoor weathering resistance and also in their
ageing properties and flame resistance. In these properties they
are superior in some cases to the conventional polycarbonates
(bisphenol A-based homopolycarbonate).
These cocondensates are prepared starting from the monomers
industrially mostly via the interfacial process with phosgene. Also
known is the preparation of these siloxane cocondensates via the
melt transesterification process using diphenyl carbonate, A
disadvantage of these processes is that the industrial plants they
utilize are used for producing standard polycarbonate and are
therefore large in size. The preparation of specific block
cocondensates in these plants is often not economically rational,
owing to the smaller volume of these products. Furthermore, the
feedstocks needed for preparing the cocondensates, such as the
polydimethylsiloxanes, for example, may adversely affect the plant,
since they can lead to fouling of the plant or of the solvent
circuits. Moreover, the preparation requires toxic feedstocks such
as phosgene or entails a high energy demand, as in the melt
transesterification process.
The preparation of polysiloxanecarbonate block copolymers via the
interfacial process is known from the literature and described for
example in U.S. Pat. Nos. 3,189,662, 3,419,634, DE 3,34,782 and EP
122,535.
The preparation of polysiloxanecarbonate block copolymers by the
melt transesterification process from bisphenol, diaryl carbonate,
silanol end-terminated polysiloxanes and catalyst is described in
U.S. Pat. No. 5,227,449. Siloxane compounds used here are
polydiphenyl- and/or polydimethyl-siloxane telomers having silanol
end groups. It is known, however, that dimethylsiloxanes of this
kind with silanol end groups, in contrast to diphenylsiloxane with
silanol end groups, exhibit an increasing tendency towards
self-condensation in an acidic or basic medium with decreasing
chain length, thereby hindering their integration into the
copolymer that forms. Cyclic siloxanes formed in this process
remain in the polymer and are exceptionally disruptive to
applications in the electricallelectronics sector.
Disadvantageous features affecting all of these processes are the
use of organic solvents in at least one step of the synthesis of
the silicone-polycarbonate block copolymers, the use of phosgene as
a feedstock, or the inadequate quality of the cocondensate. In
particular, the synthesis of the cocondensates starting from the
monomers is very costly and inconvenient, both in the interfacial
process and also, in particular, in the melt transesterification
process. in the case of melt processes, for example, a low vacuum
and low temperatures must be employed in order to prevent
evaporation and hence removal of the monomers. Only in later
reaction stages, in which oligomers with a higher molar mass have
formed, is it possible to employ lower pressures and higher
temperatures. This means that the reaction must he conducted over
several stages and the reaction times are therefore correspondingly
long.
With the aim of avoiding the disadvantages described above, other
known processes start from commercial polycarbonates. This is
described in U.S. Pat. Nos. 5,414,054 and 5,821,321, for example.
Here, a conventional polycarbonate is reacted with a specific
polyditnethylsiloxane in a reactive extrusion process. A
disadvantage of these processes is the use of highly active
transesterification catalysts, which permit production of the
cocondensates on an extruder within short residence times. These
transesterification catalysts, however, remain in the product and
cannot, or cannot adequately, be deactivated. Consequently,
injection mouldings produced from the cocondensates prepared
accordingly exhibit inadequate ageing characteristics, especially
inadequate thermal ageing characteristics. Furthermore, specific
and hence expensive siloxane blocks have to be used.
DE 19710081 describes a process for preparing the stated
cocondensates in a melt transesterification procedure, starting
from an oligocarbonate and a specific hydroxyarylsiloxane. The
preparation of the oligocarbonate as well is described in that
application. However, the large-scale preparation of
oligocarbonates for the purpose of preparing specific cocondensates
of relatively low volume is very costly and inconvenient. These
oligocarbonates have relatively low molecular weights and
relatively high OH end group concentrations. On account of their
low chain length, these oligocarbonates frequently have phenolic OH
concentrations of more than 1000 ppm. Products of this kind are
normally unavailable commercially and would have to be produced
especially, therefore, for preparing the cocondensates. It is not
economic, though, to operate large-scale industrial plants with the
production of small-volume precursor products. Furthermore,
precursor products of this kind are much more reactive than
conventional commercial products of high molecular mass based on
polycarbonate, owing to the impurities present in these products,
such as residual solvents, residual catalysts, unreacted monomers,
etc., for example. For these reasons, corresponding precursor
products or aromatic oligocarbonates suitable for the preparation
of such block cocondensates are not available commercially.
Moreover, the process presented in DE 19710081 does not allow the
preparation of block cocondensate within short reaction times. Both
the preparation of the oligocarbonate and the preparation of the
block cocondensate take place over a number of stages with
residence times totaling well above an hour. Furthermore, the
resulting material is not suitable for the preparation of
cocondensates, since the high concentration of OH end groups and
also other impurities, such as residual catalyst constituents, for
example, lead to a poor colour in the end product.
Block cocondensates of polysiloxane and copolycarbonate based on
dihydroxydiphenylcycloalkanes are known in principle. The
preparation of block cocondensates of this kind in an interfacial
process is described in EP 0374635 and DE 38 42 931. The
preparation of such block cocondensates in a melt
transesterification process or reactive extrusion process, in
contrast, is not described. The materials described in EP 0374635
are notable for high heat distortion resistance and high notched
impact strength. There is no description of the rheological
properties,
Starting from the prior art as outlined, the object, therefore, was
that of providing moulding compositions based on
siloxane-containing block cocondensates that are distinguished by
high heat distortion resistance and high notched impact strength
and that can be prepared by an improved or simplified process. The
block cocondensates are intended additionally to possess good
rheological properties.
This object has been solved by the subject matter of the
claims.
It has surprisingly been found that block cocondensates of
polysiloxanes and dihydroxydiarylcycloalkane-based
(co)polycarbonates are preparable starting from commercial
polycarbonates. Hence it is possible to avoid the use both of
phosgene and of bisphenol A and diphenyl carbonate as monomers.
Surprisingly it has emerged, furthermore, that a siloxane block
copolycarbonate obtained in a melt transesterification process and
prepared starting from copolycarbonate comprising
dihydroxydiphenylcycloalkyl derivatives does not have the good
mechanical properties described in EP 0374635. The skilled person
would assume that the process has no influence on the resultant
properties of the block cocondensate, That person would instead
expect the profile of properties to be dependent exclusively on the
composition of the block cocondensate.
Found surprisingly has been a process with which it is possible to
prepare a block cocondensate comprising siloxane blocks and
dihydroxydiphenylcycloalkane-based structural units in a melt
transesterification procedure from the corresponding polysiloxanes
and polycarbonate(s). The cocondensates feature a combination of
high notched impact strength and high heat distortion resistance.
These block cocondensates further have good rheological
properties,
The invention accordingly provides block cocondensates comprising
(A) 1-80 wt % of structural units of the general formula (1), based
on the total weight of the block cocondensate,
##STR00001## in which R.sup.1 and R.sup.2 independently of one
another are hydrogen, halogen, C.sub.1-C.sub.8 alkyl,
C.sub.5-C.sub.6 cycloalkyl, phenyl or C.sub.7-C.sub.12 aralkyl,
R.sup.3 and R.sup.4 for each X are individually selectable and
independently of one another are hydrogen or C.sub.1-C.sub.6 alkyl,
and n is an integer from 4 to 7, X is carbon, with the proviso that
on at least one atom X R.sup.3 and R.sup.4 are C.sub.1-C.sub.6
alkyl; (B) siloxane blocks of the general formula (2)
##STR00002## where R.sup.5 is H, Cl, Br, C.sub.1 to C.sub.4 alkyl
or C.sub.1 to C.sub.4 alkoxy, R.sup.6 and R.sup.7 independently of
one another are selected from aryl, C.sub.1 to C.sub.10 alkyl and
C.sub.1 to C.sub.10 alkylaryl, V is O, S, C.sub.1 to C.sub.6 alkyl
or C.sub.1 to C.sub.6 alkoxy, W is a single bond, S, C.sub.1 to
C.sub.6 alkyl or C.sub.1 to C.sub.6 alkoxy, Y is a single bond,
--CO--, --O--, C.sub.1 to C.sub.6 alkylene, C.sub.2 to C.sub.5
alkylidene, is a C.sub.5 to C.sub.6 cycloalkylidene radical which
may be substituted one or more times by C.sub.1 to C.sub.4 alkyl,
or is C.sub.6 to C.sub.12 arylene, which may he fused to a further
aromatic ring containing heteroatoms, m is an average number of
repeat units from 1 to 10, o is an average number of repeat units
from 1 to 500, and p and q are each 0 or 1; and (C)
homopolycarbonate blocks which contain no structural units of the
formula (1) and have a number-average molecular weight M.sub.n of
at least 2000 g/mol. Definitions
"C.sub.1-C.sub.4 alkyl" for the purposes of the invention is for
example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl,
tert-butyl. "C.sub.1-C.sub.6 alkyl", furthermore, is for example
n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, neopentyl,
1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl,
1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl,
4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl,
1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl,
3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl,
1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl,
1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl or
1-ethyl-2-methylpropyl, "C.sub.1-C.sub.10 alkyl", furthermore, is
for example n-heptyl and n-octyl, pinacyl, n-nonyl, n-decyl, and
C.sub.1-C.sub.34 alkyl, furthermore, is for example n-dodecyl,
n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.
The same applies in respect of the corresponding alkyl radical in
alkoxy radicals, alkylene radicals and alkylidene radicals, for
example.
"Aryl" is a carbocyclic aromatic radical having 6 to 34 skeletal
carbon atoms. The same applies to an arylene radical and also to
the aromatic moiety of an arylalkyl radical, also called aralkyl
radical, and also to aryl constituents of more complex groups, such
as arylcarbonyl radicals, for example. Examples of
"C.sub.6-C.sub.34 aryl" are phenyl, o-, p-, m-tolyl, naphthyl,
phenanthrenyl, anthracenyl or fluorenyl.
"Arylalkyl" or "aralkyl" in each case independently is a
straight-chain, cyclic, branched or unbranched alkyl radical as
defined above, which may be substituted one or more times or
completely by aryl radicals as defined above.
"Alkylaryl" is an alkyl radical as defined above bonded via an aryl
radical as defined above.
"C.sub.1-C.sub.6 alkylene" is a straight-chain or branched alkylene
radical having 1 to 6 carbon atoms.
"C.sub.2-C.sub.5 alkylidene" is a C.sub.2-C.sub.5 alkyl radical as
defined above that is bonded via a double bond.
"C.sub.6 to C.sub.12 arylene" is an arylene radical having 6 to 12
aromatic carbon atoms.
"C.sub.5 cycloalkyl" is a cyclopentanyl radical and "C.sub.6
cycloalkyl" is a cyclohexanyl radical.
"C.sub.5-C.sub.6 cycloalkylidene" is a C.sub.5-C.sub.6 cycloalkyl
radical as defined above that is doubly bonded via a carbon
atom.
The recitations above are by way of example and should not be
understood as imposing any limitation.
For the purposes of the present invention, ppb and ppm--unless
otherwise indicated--refer to parts by weight.
Furthermore, preferred embodiments stated in the present invention
can be combined with one another and should not be viewed
exclusively as an isolated modification.
Component (A)
The block cocondensate of the invention comprises as component (A)
1-80 wt % of structural units of the general formula (1), the
quantity figure being based on the total weight of the block
cocondensate.
The amount of structural units of the formula (1) is preferably 5.0
to 75 wt %, more preferably 10 to 70 wt % and very preferably 20 to
70 wt %, based in each case on the total weight of the block
cocondensate.
In particularly preferred structural units of the formula (1),
(R.sup.1 and R.sup.2 independently of one another are methyl,
phenyl or H and n is an integer from 4 to 5.
Especially preferred structural units of the general formula (1)
derive from 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane
(bisphenol TMC).
The structural units of the general formula (1) are present
preferably in the form of copolycarbonate blocks, containing the
structural units of the general formula (1), in the
cocondensate.
The copolycarbonate blocks preferably further have structural units
which derive from a diphenol of the general formula (3)
##STR00003## in which R.sup.8 and R.sup.9 independently of one
another are H, C.sub.1-C.sub.18 alkyl, C.sub.1-C.sub.18 alkoxy,
halogen or optionally substituted aryl or aralkyl, preferably H or
C.sub.1-C.sub.12 alkyl, more preferably H or C.sub.1-C.sub.8 alkyl
and very preferably H or methyl, and Z is a single bond, --CO--,
--O--, C.sub.1 to C.sub.6 alkylene, C.sub.2 to C.sub.5 alkylidene,
or is C.sub.6 to C.sub.12 arylene, which may be fused to a further
aromatic ring containing heteroatoms, and more preferably is
isopropylidene.
Suitable diphenols of the formula (3) are, for example,
hydroquinone, resorcinol, bis(hydroxyphenyl)alkanes,
bis(hydroxyphenyl) ethers, bis(hydroxyphenyl) ketones,
.alpha.,.alpha.'-bis(hydroxyphenyl)diisopropylbenzenes, and also
the alkylated, ring-alkylated and ring-halogenated compounds
thereof.
Further-preferred diphenols of the formula (3) are
4,4'-dihydroxybiphenyl, 2,2-bis(4-hydroxyphenyl)-1-phenylpropane,
1,1-bis(4-hydroxyphenyl)phenylethane,
2,2-bis(4-hydroxyphenyl)propane,
2,2-bis(3-methyl-4-hydroxyphenyl)propane,
2,4-bis(4-hydroxyphenyl)-2-methylbutane, 1,3-bis
[2-(4-hydroxyphenyl)-2-propyl]benzene (bisphenol M),
2,2-bis(3-methyl-4-hydroxyphenyl)propane,
bis(3,5-dimethyl-4-hydroxyphenyl)methane,
2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane,
2,4-bis(3,5-dimethyl-4-hydroxyphenyl)-2-methylbutane and
1,3-bis[2-(3,5-dimethyl-4-hydroxyphenyl)-2-propyl]benzene.
Particularly preferred diphenols of the formula (3) are
2,2-bis(4-hydroxyphenyl)propane (bisphenol A) and
2,2-bis(3-methyl-4-hydroxyphenyl)propane. Especially preferred is
bisphenol A.
Component (B)
The block cocondensate of the invention comprises as component (B)
siloxane blocks of the general formula (2).
In the general formula (2) R.sup.5 is preferably H or methyl, more
preferably H.
R.sup.6 and R.sup.7 are preferably methyl.
Y is preferably a single bond, --CO--, --O--, C.sub.1 to C.sub.5
alkylene, C.sub.2 to C.sub.5 alkylidene, or a C.sub.5 to C.sub.6
cycloalkylidene radical which may be substituted one or more times
by C.sub.1 to C.sub.4 alkyl, and more preferably is a single bond,
--O--, isopropylidene, or a C.sub.5 to C.sub.6 cycloalkylidene
radical which may be substituted one or more times by C.sub.1 to
C.sub.4 alkyl, and more particularly is isopropylidene.
Preferably o is an average number of repeat units from 10 to 400,
more preferably 10 to 100, very preferably 20 to 60.
Preferably m is an average number of repeat units from 1 to 6, more
preferably 2 to 5.
The product of o times m is preferably a number between 12 and 400,
more preferably 15 and 200.
Particularly preferred siloxane blocks of the formula (2) are those
in which V is O, W is a single bond and q is 0. These siloxane
blocks have the general formula (2a):
##STR00004## where R.sup.5, R.sup.6, R.sup.7, Y, o, p and m have
the same definition as in formula (2).
Especially preferred structures of the formula (2a) are those in
which
R.sup.5 is H or methyl, more preferably H,
R.sup.5 and R.sup.7 are methyl, and
Y is a single bond, --O--, isopropylidene or is a C.sub.5 to
C.sub.6 cycloalkylidene radical which may be substituted one or
more times by C.sub.1 to C.sub.4 alkyl, and more particularly is
isopropylidene.
It is preferred here for m to be an average number of repeat units
from 1 to 6, preferably 2 to 5, for o to be an average number of
repeat units from 1 to 100, and for p to be 0 or 1, and for the
product of m times o to be a number between 15 and 200.
The fraction of the siloxane blocks of the formula (2), preferably
(2a), in the block cocondensate is preferably 0.5 to 20.0 wt %,
more preferably 1.0 to 10 wt %, based on the total weight of the
block cocondensate.
Component (C)
The block cocondensate of the invention comprises as component (C)
homopolycarbonate blocks which contain no structural units of the
formula (1) and which have a number-average molecular weight
M.sub.n at least 2000 g/mol.
The number-average molecular weight M.sub.n of the
homopolycarbonate blocks is preferably at least 4000 g/mol, more
preferably 5000 to 20 000 g/mol.
The homopolycarbonate blocks preferably have structural units of
the general formula (3)
##STR00005## where Z, R.sup.8 and R.sup.9 have the meaning already
defined in connection with component (A).
Particularly preferred homopolycarbonates are those based on a
diphenol selected from the group consisting of
4,4'-dihydroxybiphenyl, 2,2-bis(4-hydroxyphenyl)-1-phenylpropane,
1,1-bis(4-hydroxyphenyl)phenylethane,
2,2-bis(4-hydroxyphenyl)propane,
2,2-bis(3-methyl-4-hydroxyphenyl)propane,
2,4-bis(4-hydroxyphenyl)-2-methylbutane,
1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene (bisphenol M),
2,2-bis(3-methyl-4-hydroxyphenyl)propane,
bis(3,5-dimethyl-4-hydroxyphenyl)methane,
2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane,
bis(3,5-dimethyl-4-hydroxyphenyl) sulphone,
2,4-bis(3,5-dimethyl-4-hydroxyphenyl)-2-methylbutane and
1,3-bis[2-(3,5-dimethyl-4-hydroxyphenyl)-2-propyl]benzene.
Especially preferred are homopolycarbonates based on bisphenol
A.
The homopolycarbonate blocks which are used for the preparation
have an average molecular weight M.sub.n of at least 2000 g/mol,
measured according to gel permeation chromatography with
polycarbonate standard, and may derive from a homopolycarbonate
which has been obtained by the melt transesterification process or
by the interfacial process. The homopolycarbonate can be linear or
branched.
The homopolycarbonate blocks preferably derive from a
homopolycarbonate which has been obtained by the melt
transesterification process, referred to below as "melt
polycarbonate". It is known that a melt polycarbonate (SPC) has a
number of differences relative to a solution-prepared polycarbonate
(LPC). One difference are increased levels of phenolic OH end
groups in the case of the SPC. A further difference are the
branching-agent structures present in the SPC, which form as a
result of Fries rearrangement in the melt.
In one preferred embodiment, accordingly, the block cocondensates
of the invention have one or more branching-agent structures of the
formulae (I) to (IV),
##STR00006## where the phenyl rings are unsubstituted or
independently of one another may be substituted once or twice by
C.sub.1 to C.sub.8 alkyl and/or halogen, preferably C.sub.1 to
C.sub.4 alkyl, more preferably methyl, but are preferably
unsubstituted, X is a single bond, C.sub.1 to C.sub.6 alkylene,
C.sub.2 to C.sub.5 alkylidene or C.sub.5 to C.sub.6 cycloalkylidene
which may be substituted one or more times by C.sub.1 to C.sub.4
alkyl, and preferably is a single bond or C.sub.1 to C.sub.4
alkylene, and especially preferably is isopropylidene, and the
linkages indicated by--in the structural units (I) to (IV) are in
each case part of a carboxyl group.
The total amount of the structural units (I) to (IV) is preferably
50 to 2000 ppm, more preferably 50 to 1000 ppm, especially
preferably 80 to 850 ppm (determined by hydrolysis, based on the
homopolycarbonate blocks).
The branching-agent structures (I) to (IV) here are incorporated
into the polymer chain of the block cocondensate, preferably into
the homopolycarbonate blocks.
In order to determine the amount of the branching-agent structures,
the block cocondensate in question is subjected to total hydrolysis
so as to form the corresponding degradation products of the
formulae (Ia) to (IVa), the quantity of which is determined by
HPLC. (This may be done, for example, as follows: the polycarbonate
sample is hydrolysed under reflux using sodium methoxide. The
corresponding solution is acidified and concentrated to dryness.
The residue from drying is dissolved in acetonitrile and the
phenolic compounds of the formulae (Ia) to (IVa) are determined by
means of HPLC with UV detection.)
##STR00007##
The amount of the compound of the formula (Ia) released in this
procedure is preferably 20 to 800 ppm, more preferably 25 to 700
ppm and especially preferably 30 to 500 ppm, based on the
homopolycarbonate blocks.
The amount of the compound of the formula (IIa) released in this
procedure is preferably 0 (i.e. below the detection limit of 10
ppm.) to 100 ppm, more preferably 0 to 80 ppm and especially
preferably 0 to 50 ppm, based on the homopolycarbonate blocks.
The amount of the compound of the formula (IIIa) released in this
procedure is preferably 0 (i.e. below the detection limit of 10
ppm) to 800 ppm, more preferably 10 to 700 ppm and especially
preferably 20 to 600 ppm, and with very particular preference 30 to
350 ppm, based on the homopolycarbonate blocks.
The amount of the compound of the formula (IVa) released in this
procedure is preferably 0 (i.e. below the detection limit of 10
ppm) to 300 ppm, preferably 5 to 250 ppm and especially preferably
10 to 200 ppm, based on the homopolycarbonate blocks.
For reasons of simplification, the quantity of the structures of
the formulae (I) to (IV) is made equal to the quantity of the
compounds of the formulae (Ia) to (IVa) released.
The preparation of polycarbonates comprising the structural
elements (I) to (IV) is known from DE 102008019503.
The fraction of the structural units of the formula (3) in the
block cocondensate is preferably at least 10.0 wt %, more
preferably at least 20.0 wt %, based on the total weight of the
block cocondensate.
Process
The block cocondensates of the invention can be obtained by
reaction of the corresponding hydroxyaryloxy-terminated siloxanes
with (co)polycarbonates comprising structural units of the formula
(1) and homopolycarbonates.
A further subject of the invention is therefore a process for
preparing a block cocondensate of the invention, comprising the
reaction of (a) a (co)polycarbonate comprising structural units of
the general formula (1) (b) a hydroxyaryl-terminated polysiloxane
of the formula (2b)
##STR00008## where R.sup.5, R.sup.6, R.sup.7, V, W, Y, o, p, q and
m have the same definition as in formula (2); and (c) and a
homopolycarbonate in the melt.
The reaction takes place preferably at temperatures of 280.degree.
C. to 400.degree. C., more preferably 300.degree. C. to 390.degree.
C., with further preference of 320.degree. C. to 380.degree. C. and
very preferably of 330.degree. C. to 370.degree. C. under pressures
of 0.001 mbar to 50 mbar, preferably 0.005 mbar to 40 mbar,
especially preferably 0.02 to 30 mbar and very preferably 0.03 to 5
mbar, preferably in the presence of a catalyst.
The preparation of the block cocondensates present in accordance
with the invention requires as component (a) (co)polycarbonates
(i.e. homo- or copolycarbonates) based on bisphenols of the formula
(1') and optionally one or more further diphenols of the formula
(3)--as described in connection with component A of the block
cocondensate of the invention.
##STR00009##
One preferred embodiment uses copolycarbonates of the structure
(3c):
##STR00010## where R.sup.10 is C.sub.1 to C.sub.6 alkyl, preferably
C.sub.1 to C.sub.4 alkyl, R.sup.11 is H, n-butyl or tert-butyl,
preferably H or tert-butyl, s and t characterize mol % of the
bisphenols used and therefore s and t are each values between 0 and
1 and the sum s+t=1, and r is determined by the molecular
weight.
Especially preferred are copolycarbonates based on bisphenol A and
bisphenol TMC
(1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane).
These copolycarbonates for use in accordance with the invention
preferably have molecular weights Mw (weight average Mw, determined
by gel permeation chromatography GPC measurement) of 12 000 to 120
000 g/mol preferably of 15 000 to 80 000 g/mol, more particularly
of 18 000 to 60 000 g/mol very preferably of 18 000 to 40 000
g/mol. Molecular weights can also be specified by the number
average Mn, determined likewise by GPC after prior calibration to
polycarbonate.
The hydroxyaryloxy-terminated siloxanes of the formula (2b) that
are for use as component (b) may be obtained in accordance with the
process described in US 2013/0267665 A1.
The process of the invention prefers to use siloxanes of the
formula (2b) having a weight-average molecular weight Mw of 3000 to
20 000 g/mol, more preferably 3500 to 15 000 g/mol, determined in
each case by means of gel permeation chromatography and a bisphenol
A standard.
As component (c), use is made of homopolycarbonates having
number-average molecular weights of 2000 g/mol, preferably 6500 to
14 000 g/mol (measured according to gel permeation chromatography
with polycarbonate standard (bisphenol A-PC)). These
homopolycarbonates preferably have a phenolic OH group content of
250 ppm to 1000 ppm, preferably 300 to 900, and especially
preferably of 350 to 800 ppm.
Homopolycarbonates based on bisphenol A are used in particular.
Very preferably these homopolycarbonates comprise phenol as end
group.
Especially suitable here for preparing the block cocondensates of
the invention are homopolycarbonates which have been prepared by
the melt transesterification process. Especially preferred
polycarhonates are those whose preparation is described in DE
102008019503.
The components (a) to (c) are preferably reacted in the following
amounts with one another: (a) 20 to 94.5 wt % of (co)polycarbonate,
(b) 0.5 to 20 wt % of hydroxyaryl-terminated polysiloxane, and (c)
5 to 79.5 wt % of homopolycarbonate, based in each case on the
total weight of the melt.
Reaction preferably takes place in the presence of a phosphonium
catalyst of the formula (4)
##STR00011## in which R.sup.a, R.sup.b, R.sup.c and R.sup.d
independently of one another are C.sub.1-C.sub.10 alkyl,
C.sub.6-C.sub.14 aryl, C.sub.7-C.sub.15 arylalkyl or
C.sub.5-C.sub.6 cycloalkyl, and A--is an anion selected from the
group consisting of hydroxide, sulphate, hydrogensulphate,
hydrogencarbonate, carbonate, halogen and alkoxides, or aroxides of
the formula --OR.sup.e, where R.sup.e is C.sub.6-C.sub.14 aryl,
C.sub.7-C.sub.15 arylalkyl or C.sub.5-C.sub.6 cycloalkyl.
The homopolycarbonate used preferably has one or more
branching-agent structures of the formulae (I) to (IV), as already
defined in connection with component (C) of the block cocondensate
of the invention.
The total amount of the structural units (1) to (IV) is preferably
50 to 2000 ppm, more preferably 50 to 1000 ppm, especially
preferably 80 to 850 ppm (determined by hydrolysis, based on the
homopolycarbonate).
The branching-agent structures (I) to (IV) are incorporated here in
the polymer chain of the homopolycarbonate.
In order to determine the quantity of the branching-agent
structures, the homopolycarbonate is subjected to total hydrolysis
to form the corresponding degradation products of the formulae (Ia)
to (IVa), as already described in connection with component (C) of
the block cocondensate of the invention. The quantities of the
degradation products are determined by means of HPLC.
The amount of the compound of the formula (Ia) released in this
procedure is preferably 20 to 800 ppm, more preferably 25 to 700
ppm and especially preferably 30 to 500 ppm, based on the
homopolycarbonate.
The amount of the compound of the formula (IIa) released in this
procedure is preferably 0 (i.e. below the detection limit of 10
ppm) to 100 ppm, more preferably 0 to 80 ppm and especially
preferably 0 to 50 ppm, based on the homopolycarbonate.
The amount of the compound of the formula (IIIa) released in this
procedure is preferably 0 (i.e. below the detection limit of 10
ppm) to 800 ppm, more preferably 10 to 700 ppm and especially
preferably 20 to 600 ppm, and with very particular preference 30 to
350 ppm, based on the homopolycarbonate.
The amount of the compound of the formula (IVa) released in this
procedure is preferably 0 (i.e. below the detection limit of 10
ppm) to 300 ppm, preferably 5 to 250 ppm and especially preferably
10 to 200 ppm, based on the homopolycarbonate.
For reasons of simplification, the quantity of the structures of
the formulae (I) to (IV) is made equal to the quantity of the
compounds of the formulae (Ia) to (IVa) released.
A further subject of the invention is a block cocondensate obtained
by the process of the invention.
Moulding Compounds
The block cocondensates of the invention are suitable for producing
moulding compounds and extrudates and mouldings produced from these
compounds.
A further subject of the invention is therefore the use of the
block cocondensates for producing moulding compounds and extrudates
or mouldings produced from these compounds.
The moulding compounds may further comprise UV absorbers, mould
release agents, heat stabilizers and/or processing stabilizers, and
optionally further additives.
Examples of suitable UV absorbers are described in EP 1 308 084 A1,
in DE 102007011069 A1 and in DE 10311063 A1, for example.
Particularly suitable ultraviolet absorbers are
hydroxy-benzotriazoles, such as
2-(3',5'-bis(1,1-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole
(Tinuvin.RTM. 234, BASF AG, Ludwigshafen),
2-(2'-hydroxy-5'-(tert-octyl)phenyl)benzotriazole (Tinuvin.RTM.
329, BASF AG, Ludwigshafen),
2-(2'-hydroxy-3'-(2-butyl)-5'-(tert-butyl)phenyl)benzotriazole
(Tinuvin.RTM. 350, BASF AG, Ludwigshafen),
bis(3-(2H-benzotriazolyl)-2-hydroxy-5-tert-octyl)methane
(Tinuvin.RTM. 360, BASF AG, Ludwigshafen),
(2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyloxy)phenol
(Tinuvin.RTM. 1577, BASF AG, Ludwigshafen), and also the
benzophenones 2,4-dihydroxybenzophenone (Chimasorb.RTM. 22, BASF
AG, Ludwigshafen) and 2-hydroxy-4-(octyloxy)benzophenone
(Chimassorb.RTM. 81, Ciba, Basle), 2-propenoic acid,
2-cyano-3,3-diphenyl,
2,2-bis[[(2-cyano-1-oxo-3,3-diphenyl-2-propenyl)oxy]methyl]-1,3-propanedi-
yl ester (9CI) (Uvinul.RTM. 3030, BASF AG Ludwigshafen),
2-[2-hydroxy-4-(2-ethylhexy)oxy]phenyl-4,6-di(4-phenyl)phenyl-1,3,5-triaz-
ine (Tinuvin.RTM. 1600, BASF AG, Ludwigshafen) or tetraethyl
2,2'-(1,4-phenylenedimethylidene)bismalonate (Hostavin.RTM. B-Cap,
Clariant AG). Mixtures of these ultraviolet absorbers may also be
used.
Especially preferred UV absorbers are
2-(2'-hydroxy-5'-(test-octyl)phenyl)benzotriazole (Tinuvin.RTM.
329, BASF AG, Ludwigshafen),
bis(3-(2H-benzotriazolyl)-2-hydroxy-5-tert-octyl)methane
(Tinuvin.RTM. 360, BASF AG, Ludwigshafen) and
2-(3',5'-bis(1,1-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole
(Tinuvin.RTM. 234, BASF AG, Ludwigshafen), with
2-(3',5'-bis(1,1-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole
being especially preferred.
The UV absorbers are used preferably in an amount of 0.05 wt % to
10.00 wt %, more preferably 0.10 wt % to 1.00 wt %, very preferably
0.10 wt % to 0.50 wt % and especially preferably 0.10 wt % to 0.30
wt %, in the moulding compounds of the invention.
Suitable mould release agents are esters of aliphatic long-chain
carboxylic acids with mono- or polyhydric aliphatic and/or aromatic
hydroxyl compounds.
Aliphatic carboxylic esters used with preference are compounds of
the general formula (6):
(R.sup.12--C(.dbd.O)--O).sub.u--R.sup.13--(OH).sub.v (6) where u is
a number from 1 to 4, v is a number from 0 to 3. R.sup.12 is an
aliphatic, saturated or unsaturated, linear, cyclic or branched
alkyl radical, preferably C.sub.12-C.sub.30 alkyl radical, and
R.sup.13 is an alkylene radical, preferably C.sub.2-C.sub.20
alkylene radical, of a 1- to 4-hydric aliphatic alcohol
R.sup.13--(OH).sub.u+v.
For esters of polyhydric alcohols, there may also be free,
unesterifted OH groups present.
Examples of aliphatic carboxylic esters suitable in accordance with
the invention are as follows: glycerol monostearate, palmityl
palmitate and stearyl stearate. Mixtures of different carboxylic
esters of the formula (6) may also be used. Carboxylic esters used
with preference are esters of pentaerythritol, glycerol,
trimethylolpropane, propanediol, stearyl alcohol, cetyl alcohol or
myristyl alcohol with myristic, palmitic, stearic or montanic acid
and mixtures thereof. Particularly preferred are pentaerythritol
tetrastearate, stearyl stearate and propanediol distearate, and
mixtures thereof, and most preferably pentaerythritol
tetrastearate.
Examples of aliphatic carboxylic esters suitable in accordance with
the invention are glycerol monostearate, palmityl palmitate and
stearyl stearate. Mixtures of different carboxylic esters can also
be used. Carboxylic esters used with preference are esters of
pentaerythritol, glycerol, trimethylolpropane, propanediol, stearyl
alcohol, cetyl alcohol or myristyl alcohol with myristic, palmitic,
stearic or montanic acid and mixtures thereof.
Particular preference is given to pentaerythritol tetrastearate,
stearyl stearate and propanediol distearate, and mixtures thereof.
Especially preferred is pentaerythritol tetrastearate.
The mould release agents are used preferably in concentrations of
0.00 wt % to 1.00 wt %, more preferably 0,10 wt % to 0.75 wt %,
very preferably 0.15 wt % to 0.60 wt %, and especially preferably
0.20 wt % to 0.50 wt %, based on the weight of the moulding
compound.
Suitable heat stabilizers and/or processing stabilizers are
preferably selected from the group of the phosphates, phosphines,
phosphites and phenolic antioxidants and also mixtures thereof.
They are used preferably in an amount of 0.01 wt % to 0.10 wt %,
based on the weight of the moulding compounds.
Suitable heat stabilizers are triphenyl phosphite, diphenyl alkyl
phosphite, phenyl dialkyl phosphite, tris(nonylphenyl) phosphite,
trilauryl phosphite, trioctadecyl phosphite, distearyl
pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)
phosphite, diisodecyl pentaerythritol diphosphite,
bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite,
bis(2,4-dicumylphenyl) pentaerythritol diphosphite,
bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite,
diisodecyloxy pentaerythritol diphosphite,
bis(2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite,
bis(2,4,6-tris(tert-butylphenyl), pentaerythritol diphosphite,
tristearylsorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)
4,4'-biphenylene diphosphonite,
6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo[d,g]-1,3,2-dioxaphosp-
hocin, bis(2,4-di-cert-butyl-6-methylphenyl) methyl phosphite,
bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite,
6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenzo[d,g]-1,3,2-dioxaphos-
phocin, 2,2',2''-nitrilo[triethyl
tris(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl)phosphite],
2-ethylhexyl (3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl)
phosphite,
5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-dioxaphosphirane,
bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite,
triphenylphosphine (TPP), trialkylphenylphosphine,
bisdiphenylphosphinoethane and trinaphthylphosphine.
Especially preferred for use are triphenylphosphine (TPP),
Irgafos.RTM. 168 (tris(2,4-di-tert-butyl-phenyl) phosphite) and
tris(nonylphenyl) phosphite or mixtures thereof.
Other heat stabilizers which may be used include phenolic
antioxidants such as alkylated monophenols, alkylated
thioalkylphenols, hydroquinones and alkylated hydroquinones.
Particularly preferred for use are Irganox.RTM. 1010
(pentaerythritol 3-(4-hydroxy-3,5-di-tert-butylphenyl)propionate;
CAS: 6683-19-8) and Irganox 1076.RTM.
(2,6-di-tert-butyl-4-(octadecanoxycarbonylethyl)phenol).
Phosphate-based processing stabilizers can additionally be used.
The phosphate in this case preferably has the following structure
(7)
##STR00012## where R.sup.14, R.sup.15 and R.sup.16 independently of
one another may be H, identical or different linear, branched or
cyclic alkyl radicals, preferably C.sub.1-C.sub.18 alkyl
radicals.
Suitable phosphates are, for example, mono-, di- and trihexyl
phosphate, triisooctyl phosphate and trinonyl phosphate.
A preferred phosphate used is triisooctyl phosphate
(tris-2-ethylhexyl phosphate). Mixtures of different mono-, di- and
trialkyl phosphates may also be used.
The phosphates can be used in amounts of less than 0.05 wt %,
preferably from 0.00005 wt % to 0.05 wt %, more preferably 0.0002
to 0.05 wt %, very preferably from 0.0005 wt % to 0.03 wt % and
more particularly from 0.001 to 0.0120 wt %, based on the total
weight of the moulding compound.
The moulding compounds may comprise further additives, preferably
in amounts of 0.10 to 8.00 wt %, more preferably 0.20 to 3.00 wt
%.
The further additives are customary polymer additives, such as, for
example, the following additives described in EP-A 0 839 623, WO-A
96/15102, EP-A 0 500 496 or "Plastics Additives Handbook", Hans
Zweifel, 5th edition 2000, Hanser Verlag, Munich: flame retardants,
optical brighteners, flow improvers, inorganic pigments, colorants,
mould release agents or processing assistants.
"Colorants" for the purposes of the invention are both dyes and
pigments.
Examples of suitable colorants are sulphur-containing pigments such
as cadmium red and cadmium yellow, ferrocyanide-based pigments such
as Prussian blue, oxide pigments such as titanium dioxide, zinc
oxide, red iron oxide, black iron oxide, chromium oxide, titanium
yellow, zinc-iron-based brown, titanium-cobalt-based green, cobalt
blue, copper-chromium-based black and copper-iron-based black or
chromium-based pigments such as chromium yellow,
phthalocyanine-derived dyes such as copper phthalocyanine blue and
copper phthalocyanine green, fused polycyclic dyes and pigments
such as azo-based pigments (e.g. nickel azo yellow), sulphur-indigo
dyes, perinone-based, perylene-based, quinacridone-derived,
dioxazine-based, isoindolinone-based and quinophthalone-derived
derivatives, anthraquinone-based, heterocyclic systems.
Specific examples of commercial products are e.g. MACROLEX.RTM.
Blue RR, MACROLEX.RTM. Violet 3R, MACROLEX.RTM. Violet B (Lanxess
AG, Germany), Sumiplast.RTM. Violet RR, Sumiplast.RTM. Violet B,
Sumiplast.RTM. Blue OR (Sumitomo Chemical Co., Ltd.), Diaresin.RTM.
Violet D, Diaresin.RTM. Blue G, Diaresin.RTM. Blue N (Mitsubishi
Chemical Corporation), Heliogen.RTM. Blue or Heliogen.RTM. Green
(BASF AG, Germany).
Preferred among these are cyanine derivatives, quinoline
derivatives, anthraquinone derivatives, phthalocyanine derivatives
and perinone derivatives.
The moulding compounds may further comprise (co)polycarbonates.
Both homopolycarbonates and copolycarbonates are suitable for this
purpose. In a known way, they may be linear or branched. The
polycarbonates may be prepared in a known way by the melt
transesterification process or the interfacial process.
Particularly preferred are homo- and copolycarbonates with
structural units which derive from one or more diphenols of the
general formula (3), more particularly from bisphenol A. Especially
preferred homopolycarbonates are those based on bisphenol A.
The moulding compounds comprising the block cocondensate of the
invention are produced using commonplace incorporation techniques,
by combining, mixing and homogenizing of the individual
constituents, with the homogenizing in particular taking place
preferably in the melt under the action of shearing forces. The
combining and mixing optionally take place prior to the melt
homogenizing, using powder premixes.
It is also possible to use premixes produced from solutions of the
mixture components in suitable solvents, optionally with
homogenization in solution and subsequent removal of the
solvent.
In this context, in particular, the components of the moulding
compounds of the invention may be introduced by means of known
methods or in the form of masterbatches.
In this connection, the individual components of the moulding
compounds may be combined and mixed in customary apparatus such as
screw extruders (for example twin-screw extruders, TSE), kneaders,
or Brabender or Banbury mills, homogenized, and then extruded.
Following extrusion, the extrudate can be cooled and comminuted. It
is also possible for individual components to be mixed beforehand
and then for the remaining starting materials to be added,
individually and/or likewise in mixed form.
The moulding compounds can be processed to products or mouldings by
first, for example, extruding the moulding compounds as described
to form pellets and processing these pellets by suitable methods in
a known way to give different products or mouldings.
In this context, the moulding compounds may be converted by means,
for example, of hot compression moulding, spinning, blow moulding,
thermoforming, extrusion or injection moulding into products or
mouldings, shaped articles such as toy parts, fibres, foils, tapes,
panels such as solid panels, sandwich panels, twin-web sandwich
panels or corrugated panels, vessels, pipes or other profiles. Also
of interest is the use of multi-layer systems. Application may take
place along with or immediately after the shaping of the basic
body, by means of coextrusion or multi-component injection
moulding, for example. Application may alternatively take place to
the base body after it has been shaped, by means of lamination with
a film or by coating with a solution, for example.
Panels composed of base layer and optional outer layer/optional
outer layers (multi-layer systems) may be produced by
(co)extrusion, direct skinning, direct coating, insert moulding,
in-mould coating, or other suitable methods known to the skilled
person.
For extrusion, the moulding compound, optionally pretreated by
means of drying, for example, is supplied to the extruder and is
melted in the extruder's plastifying system. The plastics melt is
then pressed through a slot die or a sandwich panel die, during
which it is shaped, and is then brought into the desired ultimate
form in the roll nip of a polishing stack, and its, shape is set by
reciprocal cooling on polishing rolls and the ambient air. The
temperatures necessary for extruding the composition are set, in
which context it is possible usually to follow the manufacturer
specifications. Where the moulding compounds include polycarbonates
with high melt viscosity, for example, they are normally processed
at melt temperatures of 260.degree. C. to 350.degree. C., and the
cylinder temperatures of the plastifying cylinder and also the die
temperatures are set accordingly.
Through use of one or more ancillary extruders and a
multiple-manifold die, or, optionally, suitable melt adapters
upstream of a slot die, thermoplastic melts of different
composition can be mutually superposed, and multi-layer panels or
sheets can be produced accordingly (for the coextrusion, see, for
example, EP-A 0 110 221, EP-A 0 110 238 and EP-A 0 716 919; for
details of the adapter process and die process, see Johannaber/Ast:
"Kunststoff-Maschinenfuhrer", Hanser Verlag, 2000 and in
Gesellschaft Kunststofftechnik: "Coextrudierte Folien and Platten:
Zukunftsperspektiven, Anforderungen, Anlagen and Herstellung,
Qualitatssicherung", VDI-Verlag, 1990).
With the thermoplastic substrates described above, mouldings can
also be produced by injection moulding. The techniques for this are
known and are described in "Handbuch Spritzgiessen", Friedrich
Johannnaber/Walter Michaeli, Munich; Vienna: Hanser, 2001, ISBN
3-446-15632-1 or "Anleitung zum Bau von Spritzgiesswerkzeugen",
Menges/Michaeli/Mohren, Munich; Vienna: Hanser, 1999, ISBN
3-446-21258-2.
Injection moulding is a shape conversion process which is used in
plastics processing.
By this process, directly usable mouldings in large numbers can be
produced economically. Using an injection moulding machine, the
material in question, or the moulding compound, is plastified in an
injection unit and injected into an injection mould. The inner
chamber--the cavity--of the mould determines the shape and the
surface structure of the completed component.
Injection moulding here encompasses all injection moulding methods,
including multi-component injection moulding and injection
compression moulding methods.
Plastics mouldings are produced using the injection moulding and
injection compression moulding variants that are known within
plastics processing. Conventional injection moulding processes
without injection compression moulding technology are used in
particular for producing relatively small injection-moulded parts,
where the flow pathways are short and only moderate injection
pressures need be operated. With conventional injection moulding
processes, the plastics compound is injected into a cavity formed
between two closed mould plates whose position is fixed, and the
compound solidifies within said cavity.
Injection compression moulding processes differ from conventional
injection moulding processes in that the injecting and/or
solidifying operation is carried out with movement of the mould
plates. With the known injection compression moulding process, the
mould plates are opened a little even before the injecting
operation, in order to compensate the contraction that occurs in
the course of the subsequent solidification, and to reduce the
injection pressure required. Even at the start of the injecting
operation, therefore, a pre-enlarged cavity is present. Flash faces
of the mould guarantee that the pre-enlarged cavity is sufficiently
leakproof even when the mould plates have been opened somewhat. The
plastics compound is injected into this pre-enlarged cavity, and
during this procedure or subsequently, is subjected to pressure as
the mould moves towards closure. Injection compression moulding
technology is more complicated, but is preferred or sometimes
essential in particular in the production of mouldings with large
surface areas and thin walls, with long flow pathways. This is the
only way of reducing the injection pressures required for large
mouldings. Furthermore, injection compression moulding can be used
to avoid stresses and/or distortion in the injection moulding,
caused by high injection pressures. This is particularly important
in the production of optical plastics applications, such as glazing
(windows) in motor vehicles, for example, since optical plastics
applications entail compliance with exacting requirements with
regard to absence of stress.
Products, mouldings or shaped articles preferred in accordance with
the invention are panels, foils, pipes, glazing, car windows for
example, windows of rail and air vehicles, car sunroofs, safety
panes, roofing or glazing for buildings, lamp covers for the
interior of vehicles and buildings, lamp covers for the exterior,
such as covers of street lamps, for example, visors, spectacles,
extrusion films and solution films for displays or electrical
motors, and also ski foils, traffic-signal housings, traffic-signal
coverings, traffic-signal lenses, comprising the moulding compounds
of the invention. Not only solid panels but also twin-web sandwich
panels or multi-web sandwich panels may be used here. As further
components of the products of the invention, in addition to the
moulding compounds of the invention, further parts made of material
may be present in the products of the invention. For example,
glazing systems may have sealing materials at the edge of the
glazing. Roofing systems may have, for example, metal components
such as screws, metal pins or the like, which may serve for the
fastening or guiding (in the case of folding or sliding roofs) of
the roofing elements. Furthermore, other materials may be joined
with the moulding compounds of the invention, as in 2-component
injection moulding, for example. In this way the component in
question having IR-absorbing properties may be provided with an
edge which serves, for example, for adhesive bonding.
The invention is described in more detail below with reference to
working examples, with the determination methods described here
being employed for all corresponding variables in the present
invention, unless a description has been given to the contrary.
EXAMPLES
Materials:
PC 1:
Linear bisphenol A homopolycarbonate with end groups based on
phenol and with a melt volume rate (MVR) of 17cm.sup.3/10 min.,
measured at 250.degree. C. and 2.16 kg loading to ISO 1133, and a
number-average molecular weight M.sub.n of about 8100 g/mol. The
polycarbonate possesses a relative solution viscosity of 1.205.
This polycarbonate contains no additives such as UV stabilizers,
mould release agents or heat stabilizers. The polycarbonate was
prepared via a melt transesterification process as described in DE
102008019503.
PC 2:
Linear bisphenol A homopolycarbonate with end groups based on
phenol and with a melt volume rate (MVR) of 6 cm.sup.3/10 min,
measured at 300.degree. C. and 1.2 kg loading to ISO 1133, and a
number-average molecular weight M.sub.n of about 13 100 g/mol. This
polycarbonate contains no additives such as UV stabilizers, mould
release agents or heat stabilizers. The polycarbonate is prepared
via the interfacial process.
CoPC 1
Linear copolycarbonate based on bisphenol A (58 wt %) and bisphenol
TMC (42 wt %), with end groups based on phenol and with a melt
volume rate (MVR) of 18 cm.sup.3/10 min, measured at 330.degree. C.
and 2.16 kg loading to ISO 1133. The product contains
triphenylphosphine and pentaerythritol tetrastearate.
Copolycarbonates of this kind are available under the trade name
Apec.RTM. from Bayer MaterialScience.
CoPC 2
Linear copolycarbonate based on bisphenol A (57 wt %) and bisphenol
TMC (43 wt %), with end groups based on phenol and with a melt
volume rate (MVR) of 9.5 cm.sup.3/10 min, measured at 330.degree.
C. and 2.16 kg loading to ISO 1133). The product contains
triphenylphosphine. Copolycarbonates of this kind are available
under the trade name Apec.RTM. from Bayer MaterialScience.
Siloxane component:
Siloxane used is hydroquinone-terminated polydimethylsiloxane of
the formula (2 b) (i.e. R.sup.5=H, R.sup.6, R.sup.7=methyl, p=0,
o=15, m=3-4), The preparation of the siloxane is described in DE
19710081, for example. The molecular weight is Mw=3700 g/mol
(determined via gel permeation chromatography with bisphenol A
standard).
Catalyst:
Catalyst used is tetraphenylphosphonium phenolate from the company
Rhein Chemie Rheinau GmbH (Mannheim, Germany). The substance is
used in the form of a solid solution with phenol and contains
approximately 70 wt % tetraphenylphosphonium phenolate. The
quantities below relate to the substance obtained from Rhein Chemie
(as a solid solution with phenol).
Determination of the Solution Viscosity (eta rel):
The relative solution viscosity (.eta..sub.rel; also referred to as
eta rel) was determined an Ubbelohde viscometer in dichloromethane
at a concentration of 5 g/l at 25.degree. C.
Determination of the Melt Viscosity
The flow characteristics are determined via determination of the
melt viscosity by means of a cone/plate viscometer. The viscosity
value at low shear and at high shear is employed:
The melt viscosities were determined using a Physica UDS 200 rotary
oscillation rheometer. A cone/plate geometry was used. The cone
angle is 2.degree. and the cone diameter runs to 25 mm (MK 216). In
the case of evaporation residues, the samples were first dried in a
vacuum drying cabinet at 80.degree. C. and then pressed to thin
films with a hot press at 230.degree. C. Isothermal frequency
spectra of the complex shear modulus G*=G'+iG'' were recorded at 10
K intervals in the temperature range from 330.degree. C. to
260.degree. C. The measuring temperature was then lowered in 10 K
steps. The deformation was recorded at 10%. A spectrum from 75 to
0.08 Hz (20 measurement points) was measured in each case.
Determination of the Notched Impact Strength
The notched impact test is carried out by a method based on the
Charpy notched impact test.
The test was carried out in accordance with DIN EN ISO 179 using a
falling-weight apparatus, on test dumbbells measuring
80.times.10.times.3 mm with a 2 mm V-shaped notch. The impact is on
the narrow side opposite the notch (notch in tensile zone); the
height of fall is 0.5 m; the falling weight is 1.86 kg. The
distance between the mounts is 40 mm.
Example 1
Preparation of a Block Copolycarbonate of the Invention
A 250 ml glass flask with stirrer and short-path separator is
charged with 119.96 g of copolycarbonate (CoPC 1), 30.0 g of
polycarbonate pellets (PC 1), 7.5 g of siloxane (5 wt %) and 0.055
g (0.025 wt %) of tetraphenylphosphonium phenolate solid solution.
The apparatus is evacuated and blanketed with nitrogen (3.times. in
each case). The mixture is melted by means of a metal bath
preheated to 350.degree. C., under standard pressure (under
nitrogen) over the course of 30 minutes. Then vacuum is applied.
The pressure in the apparatus is approximately 1.5 mbar. The
reaction mixture is held in this vacuum with stirring for 30
minutes. This is followed by blanketing with nitrogen, and the
polymer melt is removed. An opaquely white polymer is obtained. The
solution viscosity is reported in Table 1.
Example 2
Preparation of a Block Copolycarbonate of the Invention
A 250 ml glass flask with stirrer and short-path separator is
charged with 120.7 g of copolycarbonate (CoPC 1), 22.5 g of
polycarbonate pellets (PC 1), 6.75 g of siloxane (4.5 wt %) and
0.0375 g (0.025 wt %) of tetraphenylphosphonium phenolate solid
solution. The apparatus is evacuated and blanketed with nitrogen
(3.times. in each case). The mixture is melted by means of a metal
bath preheated to 350.degree. C., under standard pressure (under
nitrogen) over the course of 30 minutes. Then vacuum is applied.
The pressure in the apparatus is approximately 1.5 mbar. The
reaction mixture is held in this vacuum with stirring for 30
minutes. This is followed by blanketing with nitrogen, and the
polymer melt is removed. An opaquely white polymer is obtained. The
solution viscosity is reported in Table 1.
Example 3
Preparation of a TMC-Containing Block Cocondensate (Comparative,
Without Homopolycarbonate Blocks)
A 250 ml glass flask with stirrer and short-path separator is
charged with 189.95 g of copolycarbonate (CoPC 1), 10.0 g of
siloxane (5.0 wt %) and 0.071 g (0.025 wt %) of
tetraphenylphosphonium phenolate solid solution. The apparatus is
evacuated and blanketed with nitrogen (3.times. in each case). The
mixture is melted by means of a metal bath preheated to 350.degree.
C., under standard pressure (under nitrogen) over the course of 10
minutes. Then vacuum is applied. The pressure in the apparatus is
approximately 1.5 mbar. The reaction mixture is held in this vacuum
with stirring for 30 minutes. This is followed by blanketing with
nitrogen, and the polymer melt is removed. An opaquely white
polymer is obtained. The solution viscosity is reported in Table
1.
Example 4
(Comparative, Without Siloxane Blocks, Without Homopolycarbonate
Blocks)
Corresponds to CoPC 1
Example 5
Preparation of a Blend of BPA-Based Homopolycarbonate PC 2 and
Copolycarbonate CoPC 2 (Comparative, Without Siloxane Blocks)
85 wt % of CoPC 2 and 15 wt % of PC 2 are weighed out in a 250 ml
glass flask with stirrer. The apparatus is evacuated and blanketed
with nitrogen (3.times. in each case). The mixture is melted by
means of a metal bath preheated to 350.degree. C., under standard
pressure (under nitrogen) over the course of 10 minutes. The melt
is stirred under standard pressure for 15 minutes. This is followed
by blanketing with nitrogen, and the polymer melt is removed. A
transparent polymer is obtained. The properties are reported in
Table 1.
TABLE-US-00001 TABLE 1 Example 4 Example 3 (comparative, Example 5
Example 1 Example 2 (comparative, without siloxane, (comparative,
(inventive) (inventive) without homo-PC) without homo-PC) without
siloxane) Tg (DSC) [.degree. C.] 179 181 185 187 180 Notched impact
46.1 tough 44.2 tough 20.4 brittle 5.1 brittle 9.7 brittle Charpy
A.sub.k [kJ/m.sup.2] Solution viscosity 1.301 1.327 1.307 1.25
1.284 eta rel Viscosity [Pas] 1370 1940 2160 910 834 (Circular
freq.: 1/s) Viscosity [Pas] 373 593 587 about 470 450 (Circular
freq.: 500/s)
It is seen that the moulding compounds of the invention exhibit a
tough behaviour in the notched impact test (Examples 1 and 2).
TMC-containing copolycarbonates, for their part, exhibit a brittle
behaviour in the notched impact test (Example 4). From experience,
blends of homopolycarbonate and TMC-containing copolycarbonate also
exhibit brittle behaviour over wide mixing ranges. Surprisingly,
the behaviour of a siloxane-containing block copolymer which has
been obtained by a different process, without using the
homopolycarbonate PC 1, is likewise brittle (Example 3).
Relative to the prior art, furthermore, the moulding compounds of
the invention also display advantages in flowability. Despite the
fact that the block polycarbonate of the invention from Example 1
has a higher molecular weight in comparison to the copolycarboriate
from Example 4 or to the blend from Example 5 (as indicated by the
higher solution viscosity and the higher zero-shear viscosity), the
flowability under shear is, surprisingly, better. Accordingly, the
moulding compounds of the invention display distinct advantages in
terms of both mechanical and rheological properties.
* * * * *